Diazonium Chemistry Research Articles

Chemical Patterning of Graphene, Graphite and MoS2: From Microscale to Nanoscale

Chemical patterning of 2D materials is relevant in several different domains of science and technology with exciting possibilities in electronics, catalysis, sensing, and photonics. Despite intense efforts, spatially controlled, (multifunctional) covalent chemical patterning of graphene and related 2D materials is not straightforward. In my talk, I will present examples of covalent chemical patterning of graphene, graphite and MoS2 using diazonium chemistry. In the first case, spatially resolved multicomponent covalent chemical patterning of single layer graphene was achieved using a facile and efficient method. Three different functional groups could be covalently attached to the basal plane in dense, well-defined micrometer wide patterns using a combination of lithography and a self-limiting variant of diazonium chemistry requiring no need for graphene activation. The layer thickness of the covalent films could be controlled down to 1 nm. In the second case, i will present sub-10 nm chemical patterning of graphite achieved using the electrochemical diazonium chemistry. Here, an elegant combination of covalent and non-covalent chemistry was used to achieve 5-6 nm wide linear chemical patterns with excellent pattern transfer fidelity. In the last example, I will briefly share our initial results on the nanoscale chemical patterning of MoS2 using electrochemical diazonium chemistry. Throughout the discussion, i will highlight the critical role of scanning probe microscopy, namely STM, AFM and AFM-IR in providing critical spatial and spatio-chemical information at the nano and micrometer scale where conventional analytical techniques fail to provide accurate information.

Functionalization of PEDOT:PSS for aptamer-based sensing of IL6 using organic electrochemical transistors

Here we propose a strategy to functionalize poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) based organic electrochemical transistors (OECTs) for sensing the inflammatory cytokine interleukin 6 (IL6). For this aim we use diazonium chemistry to couple 4-aminobenzoic acid to sulfonate moieties on the PSS, which can act as anchors for aptamers or other recognition elements (e.g., fluorescent, or redox probes). We investigated this approach with a commercial screen-printable PEDOT:PSS formulation but also studied the effect of PEDOT to PSS ratio as well as the amount of crosslinker in other PEDOT:PSS formulations. For screen printed OECTs, it was possible to distinguish between IL6 and bovine serum albumin (BSA) in buffer solution and detect IL6 when added in bovine plasma in the nanomolar range. Furthermore, functionalization of PEDOT:PSS formulations with higher PSS content (compared to the “standard” solutions used for OECTs) combined with frequency dependent measurements showed the potential to detect IL6 concentrations below 100 pM.

Acetylcholinesterase and butyrylcholinesterase co-immobilized on acopper containing Prussian blue modified electrode for the broad screening of insecticides.

We have developed a bienzymatic biosensor that contains acetylcholinesterase together with butyrylcholinesterase co-immobilized on the same electrode modified with a stabilized copper containing Prussian blue electrodeposited on electrodes coated with 4-aminothiophenol monolayer using diazonium chemistry and copper nanoparticles for improved sensitivity. There are organophosphorus and carbamate neurotoxic insecticides that inhibit only one of the two enzymes, e.g., pirimicarb inhibits butyrylcholinesterase at much lower concentrations than acetylcholinesterase while methomyl inhibits only acetylcholinesterase. Our system is simple and in a single measurement provides a sensitive signal for insecticides' presence based on the inhibition of the enzyme with the highest affinity for each toxic compound. The limits of detection are 50ng/mL pirimicarb for thebienzymatic biosensor in comparison with 400ng/mL pirimicarb for theacetylcholinesterase biosensor and 6ng/mL methomyl for thebienzymatic biosensor, while inhibition is obtained forthe butyrylcholinesterase biosensor at 700ng/mL.

Scalable multifunctional MOFs-textiles via diazonium chemistry

Cellulose fiber-based textiles are ubiquitous in daily life for their processability, biodegradability, and outstanding flexibility. Integrating cellulose textiles with functional coating materials can unlock their potential functionalities to engage diverse applications. Metal-organic frameworks (MOFs) are ideal candidate materials for such integration, thanks to their unique merits, such as large specific surface area, tunable pore size, and species diversity. However, achieving scalable fabrication of MOFs-textiles with high mechanical durability remains challenging. Here, we report a facile and scalable strategy for direct MOF growth on cotton fibers grafted via the diazonium chemistry. The as-prepared ZIF-67-Cotton textile (ZIF-67-CT) exhibits excellent ultraviolet (UV) resistance and organic contamination degradation via the peroxymonosulfate activation. The ZIF-67-CT is also used to encapsulate essential oils such as carvacrol to enable antibacterial activity against E. coli and S. aureus. Additionally, by directly tethering a hydrophobic molecular layer onto the MOF-coated surface, superhydrophobic ZIF-67-CT is achieved with excellent self-cleaning, antifouling, and oil-water separation performances. More importantly, the reported strategy is generic and applicable to other MOFs and cellulose fiber-based materials, and various large-scale multi-functional MOFs-textiles can be successfully manufactured, resulting in vast applications in wastewater purification, fragrance industry, and outdoor gears.

Single walled carbon nanotubes covalently functionalized by a ruthenium complex for photocatalytic oxidations

The covalent bonding of a ruthenium bipyridine complex derivative with the aromatic network of single walled carbon nanotubes (SWNT) through a stepwise protocol is presented, thus yielding the sample SWNT-Ru. To do that, an-amino decorated phenanthroline is bonded to the nanotube by means of the diazonium chemistry protocol, providing anchoring points for discrete organometallic units as depicted by the solid characterization techniques employed. The hybrid material, able to emit upon excitation, is active in the visible light-driven photocatalytic oxidation of organic sulfides to sulfoxides. SWNT-Ru presents a wide scope being able to convert more than 10 substrates with different characteristics, including added-value chemicals, with a stable performance over more than 6 cycles without metal leaching and enhanced activity compared to related homogeneous complexes. A versatile character is also demonstrated since this hybrid catalyst follows both possible photooxidation mechanisms.

Anchored silver-palladium aerogel on carbon cloth via diazonium chemistry for electrochemical reduction of CO2

Electrochemical CO2 reduction reaction (eCO2RR) is a promising route for removal of CO2 from the atmosphere and transforming it into value-added products. The development of new and efficient catalysts plays a vital role in this regard. Here a combination of carbon grafting and bimetallic metal aerogel is presented as a catalyst for eCO2RR. The grafted surface plays an essential function in assembling the catalyst on the carbon cloth (CC) surface as a supported catalyst. Herein, we describe the use of para-aminothiophenol (p-TP) as a grafting agent combined with diazonium chemistry to fix a metallic aerogel catalyst on CC as support. The silver, palladium and bi-metallic silver-palladium aerogels (Ag-p-TP, Pd-p-TP, and AgPd-p-TP) anchored onto the surface of CC yielding the corresponding surface-bound materials were used for testing the electrochemical reduction of CO2. The mono-metallic Ag carbon cloth (Ag-p-TP/CC) exhibited the ability in reducing CO2 to CO with moderate Faradaic efficiency (FE) of 74 % in 0.1 M, NaHCO3 electrolyte at pH = 7.5. The bimetallic AgPd-p-TP-CC further enhanced the Faradaic efficiency for CO formation to 88.7 %, with an unexpectedly low onset potential of −0.09 V vs. RHE. Surprisingly, formate was identified to be the liquid product when Pd-p-TP-CC and AgPd-p-TP-CC were used, with maximal FEformate of 19.0 % and 25.7 % at −1.0 V vs. RHE, respectively. In contrast, CC lacking the chemical grafting that allows immobilization of the metal aerogel (Ag-Pd/CC) exhibits lower FEco% for eCO2RR, highlighting the importance of this chemical modification of the carbon cloth surface. Diazonium chemistry coupled with metal aerogels is a new approach to generating surface-bound catalysts for the effective reduction of CO2.

Functionalizing Carbon Substrates with a Covalently Attached Cobalt Redox Buffer for Calibration-Free Solid-Contact Ion-Selective Electrodes.

With a view to potentiometric sensing with minimal calibration requirements and high long-term stability, colloid-imprinted mesoporous (CIM) carbon was functionalized by the covalent attachment of a cobalt redox buffer and used as a new solid contact for ion-selective electrodes (ISEs). The CIM carbon surface was first modified by electroless grafting of a terpyridine ligand (Tpy-ph) using diazonium chemistry, followed by stepwise binding of Co(II) and an additional Tpy ligand to the grafted ligand, forming a bis(terpyridine) Co(II) complex, CIM-ph-Tpy-Co(II)-Tpy. Half a molar equivalent of ferrocenium tetrakis(3-chlorophenyl)borate was then used to partially oxidize the Co(II) complex. Electrodes prepared with this surface-attached CIM-ph-Tpy-Co(III/II)-Tpy redox buffer as a solid contact were tested as K+ sensors in combination with valinomycin as the ionophore and Dow 3140 silicone or plasticized poly(vinyl chloride) (PVC) as the matrixes for the ion-selective membrane (ISM). This solid contact is characterized by a redox capacitance of 3.26 F/g, ensuring a well-defined interfacial potential that underpins the transduction mechanism. By use of a redox couple as an internal reference element to control the phase boundary potential at the interface of the ISM and the CIM carbon solid contact, solid-contact ion-selective electrodes (SC-ISEs) with a standard deviation of E° as low as 0.3 mV for plasticized PVC ISMs and 3.5 mV for Dow 3140 silicone ISMs were obtained. Over 100 h, these SC-ISEs exhibit an emf drift of 20 μV/h for plasticized PVC ISMs and 62 μV/h for silicone ISMs. The differences in long-term stability and reproducibility between electrodes with ISMs comprising either a plasticized PVC or silicone matrix offer valuable insights into the effect of the polymeric matrix on sensor performance.

Nitrate reduction enables safer aryldiazonium chemistry.

Aryldiazonium salts remain a staple in organic synthesis and are still prepared largely in accord with the protocol developed in the 19th century. Because of the favorable reactivity that often cannot be achieved with other aryl(pseudo)halides, diazonium chemistry continues to grow. Facile extrusion of dinitrogen contributes to the desired reactivity but is also reason for safety concerns. Explosions have occurred since the discovery of these reagents and still result in accidents. In this study, we report a diazonium chemistry paradigm shift based on nitrate reduction using thiosulfate or dihalocuprates as electron donors that avoids diazonium accumulation. Because nitrate reduction is rate-limiting, aryldiazoniums are produced as fleeting intermediates, which results in a safer and often more efficient deaminative halogenation in a single step from anilines.

One-step photo-induced modification of carbon nanotubesviapolymeric diazonium chemistry

A novel strategy for the preparation of CNT–polymer composites in a one-step photo-induced route was proposed based on polymeric diazonium chemistry, notable for its universality in both aqueous and organic solutions.

Enhancing the Photocatalytic Activity via Direct Covalent Functionalization in Single‐Walled Carbon Nanotubes

AbstractHerein, the direct covalent functionalization of single‐walled carbon nanotubes (SWNT) is presented with an amino‐decorated phenyl‐phenothiazine (PTH‐NH2) organophotocatalyst through the diazonium chemistry protocol. Three different SWNT‐PTH hybrids are prepared by varying the amount of PTH‐NH2 and diazonium agent and are fully characterized. These hybrids differ not only in the degree of functionalization, but also in the chemical structure and the photophysical properties. The study shows that these features affect the photoredox activity of the materials in the photo‐debromination of aromatic halides. Thus, sample SWNT‐PTH‐5, a functionalized nanotube with a 5% wt loading of PTH, surpasses the catalytic performance of homogeneous PTH in 11 different substrates, finishing the reaction in shorter times, in a recyclable manner and without catalyst leaching. This study demonstrates the importance of controlling the functionalization degree of SWNT with photocatalysts to prepare photocatalytic materials with even higher catalytic activity than that presented by the homogeneous PTH catalyst.

Solvent Isotope Effects on the Creation of Fluorescent Quantum Defects in Carbon Nanotubes by Aryl Diazonium Chemistry.

The integration of aryl diazonium and carbon nanotube chemistries has offered rich and versatile tools for creating nanomaterials of unique optical and electronic properties in a controllable fashion. The diazonium reaction with single-wall carbon nanotubes (SWCNTs) is known to proceed through a radical or carbocation mechanism in aqueous solutions, with deuterated water (D2O) being the frequently used solvent. Here, we show strong water solvent isotope effects on the aryl diazonium reaction with SWCNTs for creating fluorescent quantum defects using water (H2O) and D2O. We found a deduced reaction constant of ∼18.2 times larger value in D2O than in H2O, potentially due to their different chemical properties. We also observed the generation of new defect photoluminescence over a broad concentration range of diazonium reactants in H2O, as opposed to a narrow window of reaction conditions in D2O under UV excitation. Without UV light, the physical adsorption of diazonium on the surface of SWCNTs led to the fluorescence quenching of nanotubes. These findings provide important insights into the aryl diazonium chemistry with carbon nanotubes for creating promising material platforms for optical sensing, imaging, and quantum communication technologies.

Modulating pro-adhesive nature of metallic surfaces through a polypeptide coupling via diazonium chemistry

The design of biomaterials able to facilitate cell adhesion is critical in the field of tissue engineering. Precise control of surface chemistry at the material/tissue interface plays a major role in enhancing the interactions between a biomaterial and living cells. Bio-integration is particularly important in case of various electrotherapies, since a close contact between tissue and electrode's surface facilitates treatment. A promising approach towards surface biofunctionalization involves the electrografting of diazonium salts followed by the modification of organic layer with pro-adhesive polypeptides. This study focuses on the modification of platinum electrodes with a 4-nitrobenzenediazonium layer, which is then converted to the aminobenzene moiety. The electrodes are further biofunctionalized with polypeptides (polylysine and polylysine/laminin) to enhance cell adhesion. This study also explores the differences between physical and chemical coupling of selected polypeptides to modulate pro-adhesive nature of Pt electrodes with respect to human neuroblastoma SH-SY5Y cells and U87 astrocytes. Our results demonstrate the significant enhancement in cell adhesion for biofunctionalized electrodes, with more amplified adhesion noted for covalently coupled polypeptides. The implications of this research are crucial for the development of more effective and functional biomaterials, particularly biomedical electrodes, which have the potential to advance the field of bioelectronics and improve patients' outcomes.

Machine-Learning Aided NO2 Discrimination with an Array of Graphene Chemiresistors Covalently Functionalized by Diazonium Chemistry.

Boosted by the emerging need for highly integrated gas sensors in IoT ecosystems, electronic noses (e-noses) are gaining interest for the detection of specific molecules over a background of interfering gases. The sensing of nitrogen dioxide (NO2) is particularly relevant for applications in environmental monitoring and precision medicine. Here we present an easy and efficient functionalization procedure to covalently modify graphene layers, taking advantage of diazonium chemistry. Separate graphene layers were functionalised with one of three different aryl rings 4-nitrophenyl, 4-carboxyphenyl, and 4-bromophenyl). The distinct mod(ified graphene layers were assembled with a pristine layer into an e-nose for NO2 discrimination. A remarkable sensitivity to NO2 is demonstrated through exposures to gaseous solutions with NO2 concentrations in the 1-10 ppm range at room temperature. Then, the discrimination capability of the sensor array is tested by carrying out exposures to several interfering gases and analyzing the data through multivariate statistical analysis. This analysis shows that the e-nose can discriminate NO2 among all the interfering gases in a two-dimensional principal component analysis space. Finally, the e-nose is trained to accurately recognize NO2 contributions with a linear discriminant analysis approach, thus providing a metric for discrimination assessment with a prediction accuracy above 95%.

(Invited) Microenvironment Responsiveness of Defect Photoluminescence of Locally Functionalized Single-Walled Carbon Nanotubes and Its Sensing Applications

Photoluminescence (PL) of single-walled carbon nanotubes (SWCNTs) in the near infrared (NIR) region is applicable to advanced optical applications such as bio-imaging and sensing. Local chemical functionalization (slight amount of chemical modification) of SWCNTs has been developed to introduce sp3 carbon defects in the sp2 carbon network of the tube walls for the luminescent defect formation.[1-3] The resultant locally functionalized SWCNTs (lf-SWCNTs) show defect PL (E 11* PL) with red-shifted wavelengths and increased quantum yields compared to original E 11 PL of pristine SWCNTs. For lf-SWCNTs, molecularly designed modifier molecules have enabled the defect PL wavelength modulation[4] and the sensing function creation.[5,6]Recently, we have reported the unique microenvironment responsiveness of defect PL of lf-SWCNTs; namely, the greater wavelength shifts of E 11* PL than E 11 PL by dielectric effects[7] and the PL shifting behavior modulation based on the chemical structure difference of the functionalized sites and the exciton localization effects[8] were observed. The microenvironment responsiveness of the defect PL was applied to the biological sensing application development.[9] To investigate protein detection/recognition functions of lf-SWCNTs, we introduced an avidin-biotin interaction with a selective and strong binding fashion at the functionalized sites of lf-SWCNTs. The lf-SWCNTs tethering biotin groups (lf-SWCNTs-b) were synthesized through diazonium chemistry, followed by its subsequent-modification. When neutravidin was mixed with a lf-SWCNTs-b solution, E 11* PL peak was red-shifted, indicating the higher polarity environment formation by the neutravidin adsorption on lf-SWCNTs-b. When avidin or streptavidin was used, wavelength shifting behaviors of E 11* PL of lf-SWCNTs-b were clearly changed depending on the used avidin derivatives. The results indicate the different polarity environment formation deriving from structural differences of each avidin derivative. Moreover, the detection signal enhancement was observed in a film device using lf-SWCNTs-b. Therefore, lf-SWCNTs have a high potential for development of advanced protein detection/recognition systems using NIR PL.[1] T. Shiraki et al. Acc. Chem. Res., 53, 1846 (2020). [2] S. Tretiak et al., Acc. Chem. Res., 53, 1791(2020) [3] Y. Wang et al. Nat. Rev. Chem., 3, 375 (2019). [4] T. Shiraki et al. ACS Nano, DOI: 10.1021/acsnano.2c09897 (2022). [5] T. Shiraki et al. Chem. Commun., 52, 12972 (2016). [6] S. Kruss et al, Angew. Chem. Int. Ed., 59, 17732 (2020). [7] T. Shiraki et al. Chem. Commun., 55, 3662 (2019). [8] T. Shiraki et al. J. Phys. Chem. C, 125, 12758 (2021). [9] T. Shiraki et al. Nanoscale, 14, 13090 (2022). Figure 1

Improved adhesion and charge transfer between PEDOT:PSS and the surface of a platinum electrode through a diazonium chemistry route

Due to the high applicability of poly(3,4-ethylenedioxythiophene):poly(4-styrene sulfonate) (PEDOT:PSS) in organic electronics, current research is focused on providing new ways to further improve its functionality. In this paper, we have described a one-step process of electrochemical grafting of commercially available diazonium salts to the surface of a Pt electrode as a method to increase mechanical stability of PEDOT:PSS, simultaneously decreasing its charge transfer resistance and increasing capacitance. Pretreatment of Pt electrodes with electrografted layers of 4-nitrobenzene-, 4-methoxybenzene-, and 3,5-dichlorophenyl diazonium tetrafluoroborates is shown to improve charge storage capacity (235 mC/cm2 at the scan rate of 10 mV/s), decrease charge transfer resistance (15.0 ± 0.5 Ω) and enhance capacitance (13.3 ± 0.8 mF). The described method is also efficient in providing coatings with better affinity to the electrode and higher adhesion force.

Preparation of fluorine-free robust superhydrophobic fabric via diazonium radical graft polymerization

A kind of environmentally friendly superhydrophobic cotton fabric (CF) was prepared via diazonium chemistry and subsequent facile solution chemistry. Typically, a polymer layer of benzoic acid was grafted on CF surface through in-situ diazonium radical polymerization, which provided abundant active sites of carboxy group to effectively graft with fluorine-free long carbon chain alkyl groups by covalent bonding, forming hydrophobic polymer brushes on the fiber surface with great mechanical durability. Here, the effect of reaction conditions on the morphology and wettability of modified fabric surfaces were systematically investigated. In addition, the grafting mechanism of the modification was analyzed by chemical structure characterization. Owing to the synergistic effect of micro-nano roughing structures and low surface energy materials, the WCA of modified fabric was up to 156.3°, exhibiting excellent superhydrophobic performance. Compared to the pristine CF, the modified fabric well maintained its original air permeability, flexural rigidity and mechanical strength. More importantly, the superhydrophobic fabric could be against >150 min and 50 cycles of laundering and abrasion, respectively, exhibiting good mechanical durability. Even heating at 100 °C for 5 h, the prepared cotton fabric still maintained its hydrophobic properties, and the contact angle reached 154.5°. It is noteworthy that the prepared fabric could effectively separate the oil-water mixture with a separation efficiency of up to 98.4 %. Therefore, this facile grafting method opens up a new avenue to prepare fluorine-free environmentally friendly superhydrophobic fabrics.

Surface grafting of poly-L-lysine via diazonium chemistry to enhance cell adhesion to biomedical electrodes

The ability to study and regulate cell behavior at a biomaterial interface requires a strict control over its surface chemistry. Significance of studying cell adhesion in vitro and in vivo has become increasingly important, particularly in the field of tissue engineering and regenerative medicine. A promising surface modification route assumes using organic layers prepared by the method of electrografting of diazonium salts and their further functionalization with biologically active molecules as cell adhesion promoters. This work reports the modification of platinum electrodes with selected diazonium salts and poly-L-lysine to increase the number of sites available for cell adhesion. As-modified electrodes were characterized in terms of their chemical and morphological properties, as well as wettability. In order to monitor the process of cell attachment, biofunctionalized electrodes were used as substrates for culturing human neuroblastoma SH-SY5Y cells. The experiments revealed that cell adhesion is favored on the surface of diazonium-modified and poly-L-lysine coated electrodes, indicating proposed modification route as a valuable strategy enhancing the integration between bioelectronic devices and neural cells.

Chemomechanical modification of quantum emission in monolayer WSe2

Two-dimensional (2D) materials have attracted attention for quantum information science due to their ability to host single-photon emitters (SPEs). Although the properties of atomically thin materials are highly sensitive to surface modification, chemical functionalization remains unexplored in the design and control of 2D material SPEs. Here, we report a chemomechanical approach to modify SPEs in monolayer WSe2 through the synergistic combination of localized mechanical strain and noncovalent surface functionalization with aryl diazonium chemistry. Following the deposition of an aryl oligomer adlayer, the spectrally complex defect-related emission of strained monolayer WSe2 is simplified into spectrally isolated SPEs with high single-photon purity. Density functional theory calculations reveal energetic alignment between WSe2 defect states and adsorbed aryl oligomer energy levels, thus providing insight into the observed chemomechanically modified quantum emission. By revealing conditions under which chemical functionalization tunes SPEs, this work broadens the parameter space for controlling quantum emission in 2D materials.

Experimental and theoretical investigations of covalent functionalization of 1D/2D carbon-based buckypaper via aryl diazonium chemistry for high-performance energy storage

Efforts to fabricate high-conducting and high-strength free-standing graphene/carbon nanotube (CNT) buckypaper through room-temperature functionalization have been frustrated by the defective surface of the graphene and CNTs. In this study, high-quality graphene sheets were prepared via an amino-assisted liquid phase exfoliation method and used to integrate with CNTs to form free-standing flexible graphene/CNTs buckypaper. After that, individual graphene and CNT of the graphene/CNTs buckypaper were linked via diazonium chemistry to generate covalent bonds. By tuning functionalization time, the functionalized graphene/CNTs buckypaper exhibits an electrical conductivity of 87,500 S/m and a Young's modulus of 22.3 GPa, which are 6 and 10 times higher, respectively, than unfunctionalized graphene/CNTs buckypaper. Density functional theory calculations demonstrate that charge transfer rate (Ket) of the aryl linker bonded moiety configuration via covalent functionalization is an order faster than without the aryl linker bonded moiety configuration. Unprecedently, the capacitance of the functionalized graphene/CNTs buckypaper is 359.6 mF/cm3 at a scan rate of 1 mV/s with no capacitance change after 10,000 cycles of testing. This work sheds the light of the value of molecular engineering in the design of novel composite for flexible electronics, energy storage and provides important insights into the understanding of basic principles of covalent functionalization of graphene/CNTs.

Chemical Tuning of Metal Nanocatalysts Interface for ORR Electrocatalysis

AbstractA series of surface‐functionalized gold nanocatalysts are synthesized. Through diazonium chemistry, calix[4]arene molecules are grafted at the gold surface. Sharing the same anchoring function and a common backbone, the calix[4]arene ligands possess distinct terminal chemical functions where the length, hydrophobic nature, and oxygen affinity are varied. Thanks to the versatility of the calix[4]arene platform, this paper only focuses on the molecular tuning of the solid/liquid interface through the change of the tail groups while electronic effects that are regulated by the anchoring function will be similar for all catalysts. Electrocatalytic tests demonstrate the influence of the tails group on the oxygen reduction reaction performances, including efficiency, selectivity, and durability. Beyond a pure geometric steric effect, it is shown that chemical properties of the ligands can effectively tune the interactions between the metallic catalyst and the electrolyte and reactants.